作者:S.-I. Murahashi、I. Moritani、M. Nishino
DOI:10.1016/s0040-4020(01)90767-7
日期:1971.1
Photolysis of 5-diazo[a,d]cycloheptene (10) and 9-diazotribenzo[a,c,e]cycloheptene (23) in cis and trans-2-butene led stereospecifically to the formation of cyclopropane derivatives. Nonstereospecific addition of dibenzo[a,d]cycloheptenylidene could not be detected by carrying out the photolysis in a large excess of cyclohexane, or by photosensitized decomposition of 10. It is concluded that photolysis
5-重氮[a,d]环庚烯(10)和9-重氮三苯并[a,c,e]环庚烯(23)在顺式和反式-2-丁烯中的光解立体定向导致形成环丙烷衍生物。通过在大量过量的环己烷中进行光解或通过光敏分解10,无法检测到二苯并[a,d]环庚烯的非立体特异性加成。结论是10的光解会导致单峰(6)转变成三重态并与烯烃立体反应形成环丙烷。通过考虑电荷转移络合物在6与烯烃加成反应的过渡态中起重要作用,可以合理地解释这些立体化学结果。根据从ESR和光谱学获得的结果讨论了这些卡宾的电子结构。